US3839398A - Ammoxidation process - Google Patents

Ammoxidation process Download PDF

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US3839398A
US3839398A US00310306A US31030672A US3839398A US 3839398 A US3839398 A US 3839398A US 00310306 A US00310306 A US 00310306A US 31030672 A US31030672 A US 31030672A US 3839398 A US3839398 A US 3839398A
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catalyst
ammoxidation
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J Leto
J Potts
J Shang
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Sun Research and Development Co
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00Preparation of carboxylic acid nitriles
    • C07C253/24Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/28Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing six-membered aromatic rings, e.g. styrene

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  • AMMOXIDATION rRocEss Filed Nov. 29, 1972 lnited States Patent Office 3,839,398 AMMOXIDATION PROCESS Joseph R. Leto, Concord Township, and John D. Potts,
  • This invention provides a novel process for making a V204 catalyst which is integrated with the ammoxidation step of a moving-bed system and thereby achieves a highly efiicient overall ammoxidation system.
  • a significant improvement is imparted to ammoxidation reactions carried out in a moving-bed reactor using V204 as catalyst and without added oxygen by (a) separating spent catalyst consisting essentially of V202 from ammoxidation products and unreacted starting materials, (b) oxidizing a portion of said V202 to V205, (c) mixing said V205 with the remaining V202, (d) heating said mixture of V202 and V205 to a temperature of from about 350 C. to about 500 C. whereby V204 is formed, and (e) feeding said V20., to said ammoxidation for use as catalyst.
  • ammoxidation reactor is fed with ammonia and hydrocarbon reactants and also with V20.,I catalyst.
  • the V204 catalyst may be unsupported or supported on any of the conventional catalyst supports exemplified by alumina, silica, silica-alumina, and the 3,839,398 Patented Oct. l, 1974 like.
  • a supported catalyst will generally contain the catalyst at a level of from about 0.5% to about 98% by Weight, preferably at a level of about 20% to about 80% by weight of catalyst on the support.
  • the reactor is a moving-bed type which will include a moving c'uidized bed.
  • reaction products which comprise nitriles and unreacted feed materials exit from the top of the reactor together with spent catalyst which will be V202 to a large extent resulting from the reduction of the V204.
  • Catalyst and gaseous products are separated, preferably by use of a cyclone separation technique and the gaseous materials taken for further workup which will involve separation of the desired nitrile products and recycling unreacted or partially reacted materials.
  • the spent catalyst comprised of V202 will then be separated into two parts, one part, comprising about 50 mole percent, being fed into an oxidizer for conversion to V205.
  • This oxidation may be accomplished readily by passing air or other oxygen containing gas over the vanadium oxide held at about 500 C.
  • the oxidation may readily be accomplished in a cyclone which will provide intimate contact between catalyst solids and the oxidizing gas.
  • the oxidized catalyst comprising V205 is separated from the gases (again a cyclone separator is quite satisfactory) and the catalyst recombined with the remaining portion of V202. It will be understood that the V202 and V205 will be nely divided particles and will be combined in essentially stoichiometric amounts for the reaction:
  • V202 and V205 are then fed to a mixerheater where thorough mixing and the temperature is maintained between about 350 C. and 500 C. (See The ⁇ Chemistry of Titanium and Vanadium by R. J. Clark; yElsevier Publishing C0., 1968 for details of this reaction.)
  • the resulting V204 exiting from the mixerheater is then fed back into the ammoxidation reactor where the cycle begins anew.
  • the moving bed in the ammoxidation reactor may be reversed from that shown and it will also be understood that the process is useful with the numerous ammoxidation processes known in the art.
  • the organic reactants useful in the process may be selected from a wide variety of compounds and will include alkyl-substituted aromatic, aliphatic, alcyclic, and heterocyclic compounds.
  • starting materials are the monoand polyalkylsubstituted aromatic hydrocarbons such as toluene, the xylenes, mesitylene, pseudocumene, durene, pentamethylbenzene, Z-methylnaplrthalene, polymethylnaphthalenes, such as 2,6-, 2,7-, 1,5-, 1,8-, and 2,3-dimethylnaphthalene, monoalkyl and polyalkylanthracenes, and the like.
  • the alkyl substitutent may, of course, contain more than a single carbon atom and thus the corresponding ethyl, propyl, butyl, hexyl, and other alkyl substituents are also useful.
  • Aliphatic compounds normally subjected to ammoxidation include the oleiinic compounds.
  • any oleinic hydrocarbon having at least one alkyl group is useful in the process.
  • examples of such compounds are propylene, butenes, octenes, methyl heptenes, alkylbutadienes, pentadienes, ethyl butenes, hexadienes, heptadienes, and the like, all of which will give the corresponding nitriles.
  • Preferred olefins are those containing up to about ten carbon atoms, particularly propylene, butenes, and the methylbutadienes, and cycloolefinic compounds, particularly the alkylsnbstituted hydrocarbon olens exemplified by 3methylcyclohexene, 3,6-dimethy1 cyclohexene, methyltetralin, and the like.
  • alcyclic compounds hav- .ing an alkyl substituent are exemplified by methylcyclopentane, methylcyclohexane, the alkyl- ⁇ substituted tetralins, decalins, and the like.
  • heterocyclic compounds useful as organic reactants in the process will include alkyl-substituted furans, pyrroles, indoles, thiophenes, pyrazoles, imidazoles, thiazoles, oxazoles, pyrans, pyridines, quinolines, isoquinolines, pyrimidines, pyridazines, pyrazines, and the like, all of which are converted to the corresponding nitriles.
  • Preferred reactants in this group are the mono-, diand trialkyl pyridines.
  • the process will be carried out with those alkyl-substituted hydrocarbons selected from the group of benzenes and naphthalenes, and most preferably will be used to make isophthalonitrile from m-xylene, terephthalonitrile from p-xylene, and 2,6-dicyanonaphthalene from 2,6-dimethy1naphthalene.
  • alkyl-substituted hydrocarbons selected from the group of benzenes and naphthalenes, and most preferably will be used to make isophthalonitrile from m-xylene, terephthalonitrile from p-xylene, and 2,6-dicyanonaphthalene from 2,6-dimethy1naphthalene.
  • V203 for each 1659 parts by weight of V204 which enters the arnmoxidation reactor and which is entirely converted to V203, 1499 parts of V203 will be formed.
  • This V203 is divided in half, one half being oxidized with air (160 parts of oxygen gas required) for conversion to V205 (910 parts of V205 formed) and combined with the remaining half of V203 (750 parts).
  • the mixture of V203 and V205 is converted in the mixer-heater to 1659 parts of V204 which is fed back into the ammoxidation reactor.
  • This example is based on 100% conversion to the desired oxide products and does not provide for mechanical losses, but it will be understood that separate feeds of V204, V203 and V205 to the appropriate lines may be used to keep the entire system in balance.

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Abstract

1. IN THE PROCESS OF CARRYING OUT AMMOXIDATIONREACTIONS IN A MOVING BED REACTOR USING V2O4 AS CATALYST AND WITHOUT ADDED OXYGEN, THE IMPROVEMENT WHICH COMPRISES: (A) SEPARATING SPENT CATALYST CONSISTING ESSENTIALLY OF V2O3 FROM AMMOXIDATION PRODUCTS AND UNCREATED STARTING MATERIALS, (B) OXIDIZING A PORTION OFF SAID V2O3 TO V2O5, (C) MIXING SAID V2O5 WITH REMAINING V2O3, (D) HEATING SAID MIXTURE TO A TEMPERATURE BETWEEN ABOUT 350* AND 500* C. WHEREBY V2O4 IS FORMED, AND (E) FEEDING SAID V2O4 TO SAID AMMOXIDATION PROCESS FOR USE AS CATALYST.

Description

OC- l, 1974 J. R. LETo ETAL 3,839,39
AMMOXIDATION rRocEss Filed Nov. 29, 1972 lnited States Patent Office" 3,839,398 AMMOXIDATION PROCESS Joseph R. Leto, Concord Township, and John D. Potts,
Springfield, Pa., and Jer-Yu Shang, Wilmington, Del.,
assignors to Sun Research and Development Co., Philadelphia, Pa.
Filed Nov. 29, 1972, Ser. No. 310,306 Int. Cl. C07c 121/02 U.S. Cl. 260-465 C 4 Claims ABSTRACT F THE DISCLOSURE In the process of carrying out ammoxidation reactions in a moving bed reactor using V204 as catalyst, the improvement which comprises: l(a) separating spent catalyst consisting essentially of V202 from ammoxidation products and unreacted starting materials, (b) oxidizing a portion of said V205 to V205, l(c) mixing said V205 with the remaining V202, (d) heating said mixture to a temperature between about 350 to about 500 C. whereby V204 is formed, and (e) feeding said V204 to said ammoxidation process for use as catalyst.
It is known in the art of ammoxidation processes that oxides of vanadium are effective catalysts for the reaction. Thus, for example, U.S. 2,450,639' discloses V0, V02, V202 and V205 as useful ammoxidation catalysts, the preferred catalyst being V205 which is preferably preconditioned by treatment with ammonia or hydrogen. However, it has been determined recently that intermediate oxides such as V202 essentially devoid of V205 are preferred catalysts in the ammoxidation `of hydrocarbons carried out in the absence of added oxygen since such catalysts mitigate the formation of carbon oxides, thereby increasing the eciency of the reaction for the formation of nitrile products (see the application of Angstadt et al filed of even date herewith). `In using V204 in ammoxidation reactions where hydrocarbon and ammonia are reacted in the absence of added oxygen, the catalyst becomes reduced to V202 which is inactive as a catalyst. As pointed out in the above-mentioned application of Angstadt et al., it is desirable to regenerate the V204 catalyst as soon as V202 builds up to a significant amount and this is particularly true in a fixed-bed system. In moving-bed systems, however, it may not be an economic disadvantage to permit greater V202 build-up before regeneration, and, in fact, the spent portion of the catalyst may be entirely converted to V202 by the excess ammonia and hydrocarbon in the areas of the system where the ammoxidation reaction is completed.
This invention provides a novel process for making a V204 catalyst which is integrated with the ammoxidation step of a moving-bed system and thereby achieves a highly efiicient overall ammoxidation system. In accord with the invention, a significant improvement is imparted to ammoxidation reactions carried out in a moving-bed reactor using V204 as catalyst and without added oxygen by (a) separating spent catalyst consisting essentially of V202 from ammoxidation products and unreacted starting materials, (b) oxidizing a portion of said V202 to V205, (c) mixing said V205 with the remaining V202, (d) heating said mixture of V202 and V205 to a temperature of from about 350 C. to about 500 C. whereby V204 is formed, and (e) feeding said V20., to said ammoxidation for use as catalyst.
An understanding of the invention is evident from the drawing. As seen there an ammoxidation reactor is fed with ammonia and hydrocarbon reactants and also with V20.,I catalyst. The V204 catalyst may be unsupported or supported on any of the conventional catalyst supports exemplified by alumina, silica, silica-alumina, and the 3,839,398 Patented Oct. l, 1974 like. A supported catalyst will generally contain the catalyst at a level of from about 0.5% to about 98% by Weight, preferably at a level of about 20% to about 80% by weight of catalyst on the support. The reactor is a moving-bed type which will include a moving c'uidized bed. The reaction products which comprise nitriles and unreacted feed materials exit from the top of the reactor together with spent catalyst which will be V202 to a large extent resulting from the reduction of the V204. Catalyst and gaseous products are separated, preferably by use of a cyclone separation technique and the gaseous materials taken for further workup which will involve separation of the desired nitrile products and recycling unreacted or partially reacted materials.
The spent catalyst comprised of V202 will then be separated into two parts, one part, comprising about 50 mole percent, being fed into an oxidizer for conversion to V205. This oxidation may be accomplished readily by passing air or other oxygen containing gas over the vanadium oxide held at about 500 C. The oxidation may readily be accomplished in a cyclone which will provide intimate contact between catalyst solids and the oxidizing gas. The oxidized catalyst comprising V205 is separated from the gases (again a cyclone separator is quite satisfactory) and the catalyst recombined with the remaining portion of V202. It will be understood that the V202 and V205 will be nely divided particles and will be combined in essentially stoichiometric amounts for the reaction:
The mixture of V202 and V205 is then fed to a mixerheater where thorough mixing and the temperature is maintained between about 350 C. and 500 C. (See The `Chemistry of Titanium and Vanadium by R. J. Clark; yElsevier Publishing C0., 1968 for details of this reaction.) The resulting V204 exiting from the mixerheater is then fed back into the ammoxidation reactor where the cycle begins anew.
It will be understood that the moving bed in the ammoxidation reactor may be reversed from that shown and it will also be understood that the process is useful with the numerous ammoxidation processes known in the art. Thus, the organic reactants useful in the process may be selected from a wide variety of compounds and will include alkyl-substituted aromatic, aliphatic, alcyclic, and heterocyclic compounds. Among preferred starting materials are the monoand polyalkylsubstituted aromatic hydrocarbons such as toluene, the xylenes, mesitylene, pseudocumene, durene, pentamethylbenzene, Z-methylnaplrthalene, polymethylnaphthalenes, such as 2,6-, 2,7-, 1,5-, 1,8-, and 2,3-dimethylnaphthalene, monoalkyl and polyalkylanthracenes, and the like. The alkyl substitutent may, of course, contain more than a single carbon atom and thus the corresponding ethyl, propyl, butyl, hexyl, and other alkyl substituents are also useful.
Aliphatic compounds normally subjected to ammoxidation include the oleiinic compounds. Thus, any oleinic hydrocarbon having at least one alkyl group is useful in the process. Examples of such compounds are propylene, butenes, octenes, methyl heptenes, alkylbutadienes, pentadienes, ethyl butenes, hexadienes, heptadienes, and the like, all of which will give the corresponding nitriles. Preferred olefins are those containing up to about ten carbon atoms, particularly propylene, butenes, and the methylbutadienes, and cycloolefinic compounds, particularly the alkylsnbstituted hydrocarbon olens exemplified by 3methylcyclohexene, 3,6-dimethy1 cyclohexene, methyltetralin, and the like.
Also of value as reactants are alcyclic compounds hav- .ing an alkyl substituent and these compounds are exemplified by methylcyclopentane, methylcyclohexane, the alkyl- `substituted tetralins, decalins, and the like.
The heterocyclic compounds useful as organic reactants in the process will include alkyl-substituted furans, pyrroles, indoles, thiophenes, pyrazoles, imidazoles, thiazoles, oxazoles, pyrans, pyridines, quinolines, isoquinolines, pyrimidines, pyridazines, pyrazines, and the like, all of which are converted to the corresponding nitriles. Preferred reactants in this group are the mono-, diand trialkyl pyridines.
Preferably the process will be carried out with those alkyl-substituted hydrocarbons selected from the group of benzenes and naphthalenes, and most preferably will be used to make isophthalonitrile from m-xylene, terephthalonitrile from p-xylene, and 2,6-dicyanonaphthalene from 2,6-dimethy1naphthalene.
As an example to further illustrate the invention, for each 1659 parts by weight of V204 which enters the arnmoxidation reactor and which is entirely converted to V203, 1499 parts of V203 will be formed. This V203 is divided in half, one half being oxidized with air (160 parts of oxygen gas required) for conversion to V205 (910 parts of V205 formed) and combined with the remaining half of V203 (750 parts). The mixture of V203 and V205 is converted in the mixer-heater to 1659 parts of V204 which is fed back into the ammoxidation reactor. This example is based on 100% conversion to the desired oxide products and does not provide for mechanical losses, but it will be understood that separate feeds of V204, V203 and V205 to the appropriate lines may be used to keep the entire system in balance.
The invention claimed is:
1. In the process of carrying out ammoxidation reac- `tions in a moving bed reactor using V204 as catalyst and without added oxygen, the improvement which comprises:
(a) separating spent catalyst consisting essentially of V203 from ammoxidation products and unreacted starting materials,
(b) oxidizing a portion of said V203 to V205,
(c) mixing said V205 with the remaining V203,
(d) heating said mixture to a temperature between about 350 and 500 C. whereby V204 is formed, and
(e) feeding said V204 to said ammoxdation process for use as catalyst.
2. The process of Claim 1 where p-xylene is ammoxidized to terephthalonitrile.
3. The process of Claim 1 where m-xylene is ammoxidized to isophthalonitrile.
4. The process of Claim 1 where 2,6-dimethylnaphthalene is ammoxidized to 2,6-dicyanonaphthalene.
References Cited UNITED STATES PATENTS 2,450,639 10/1948 Denton 260-465 2,180,353 11/1939 Foster 252-461 LEWIS GOTT S, Primary Examiner D. H. TORRENCE, Assistant Examiner U.S. C1. X.R.
260-283 CN, 294.9, 302 R, 307 R, 309, 310 R, 319.1, 326.62, 329 R, 346.1 R, 464, 465.9; 252-461

Claims (1)

1. IN THE PROCESS OF CARRYING OUT AMMOXIDATIONREACTIONS IN A MOVING BED REACTOR USING V2O4 AS CATALYST AND WITHOUT ADDED OXYGEN, THE IMPROVEMENT WHICH COMPRISES: (A) SEPARATING SPENT CATALYST CONSISTING ESSENTIALLY OF V2O3 FROM AMMOXIDATION PRODUCTS AND UNCREATED STARTING MATERIALS, (B) OXIDIZING A PORTION OFF SAID V2O3 TO V2O5, (C) MIXING SAID V2O5 WITH REMAINING V2O3, (D) HEATING SAID MIXTURE TO A TEMPERATURE BETWEEN ABOUT 350* AND 500* C. WHEREBY V2O4 IS FORMED, AND (E) FEEDING SAID V2O4 TO SAID AMMOXIDATION PROCESS FOR USE AS CATALYST.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3981879A (en) * 1975-11-18 1976-09-21 Merck & Co., Inc. Preparation of cyanopyridines
US3990997A (en) * 1975-10-22 1976-11-09 Suntech, Inc. Method of preparing ammoxidation catalyst
US4000178A (en) * 1975-09-19 1976-12-28 Monsanto Company Paraffin ammoxidation process
US5049537A (en) * 1989-12-26 1991-09-17 Texaco Inc. Stable solid phases involving V2 O3 - TiO2 and mixtures of said phases
US5183793A (en) * 1991-11-13 1993-02-02 The Standard Oil Company Ammoxidation catalysts and methods for their preparation for use in the production of isophthalonitrile
GB2275267A (en) * 1993-02-23 1994-08-24 Basf Ag Preparation of dicyanobenzenes by ammonoxidation

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4000178A (en) * 1975-09-19 1976-12-28 Monsanto Company Paraffin ammoxidation process
US3990997A (en) * 1975-10-22 1976-11-09 Suntech, Inc. Method of preparing ammoxidation catalyst
US3981879A (en) * 1975-11-18 1976-09-21 Merck & Co., Inc. Preparation of cyanopyridines
US5049537A (en) * 1989-12-26 1991-09-17 Texaco Inc. Stable solid phases involving V2 O3 - TiO2 and mixtures of said phases
US5183793A (en) * 1991-11-13 1993-02-02 The Standard Oil Company Ammoxidation catalysts and methods for their preparation for use in the production of isophthalonitrile
GB2275267A (en) * 1993-02-23 1994-08-24 Basf Ag Preparation of dicyanobenzenes by ammonoxidation
US5554782A (en) * 1993-02-23 1996-09-10 Basf Aktiengesellschaft Preparation of dicyanobenzenes by ammonoxidation
GB2275267B (en) * 1993-02-23 1996-10-16 Basf Ag Preparation of dicyanobenzenes by ammoxidation

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